U.S. patent number 3,917,575 [Application Number 05/413,431] was granted by the patent office on 1975-11-04 for process for production of polyolefins.
This patent grant is currently assigned to Nippon Oil Co., Ltd.. Invention is credited to Nobuyuki Kuroda, Kazuo Matsuura, Masaomi Matsuzaki, Mitsuji Miyoshi.
United States Patent |
3,917,575 |
Matsuura , et al. |
November 4, 1975 |
Process for production of polyolefins
Abstract
For polymerization or copolymerization of olefins there is used
a composite catalyst comprising an organoaluminum compound and the
reaction product of an organomagnesium compound and a titanium
compound. The reaction between the organomagnesium and titanium
compounds is conducted in the presence of an ether compound, with
the molar ratio of titanium to magnesium not less than about 3 to
1. These organomagnesium, titanium and ether compounds are
selectable from wide ranges of substances specified herein.
Inventors: |
Matsuura; Kazuo (Kawasaki,
JA), Kuroda; Nobuyuki (Yokohama, JA),
Miyoshi; Mitsuji (Kanagawa, JA), Matsuzaki;
Masaomi (Yokohama, JA) |
Assignee: |
Nippon Oil Co., Ltd. (Tokyo,
JA)
|
Family
ID: |
26333318 |
Appl.
No.: |
05/413,431 |
Filed: |
November 7, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Nov 11, 1972 [JA] |
|
|
47-113218 |
Dec 22, 1972 [JA] |
|
|
48-000353 |
|
Current U.S.
Class: |
526/151; 526/348;
502/115 |
Current CPC
Class: |
C08F
10/00 (20130101); C08F 10/00 (20130101); C08F
4/6546 (20130101); C08F 10/00 (20130101); C08F
4/651 (20130101); C08F 110/02 (20130101); C08F
110/02 (20130101); C08F 2500/18 (20130101) |
Current International
Class: |
C08F
10/00 (20060101); C08F 110/02 (20060101); C08F
110/00 (20060101); C08F 004/50 (); C08F
010/02 () |
Field of
Search: |
;260/88.2,93.7,94.9DA,94.9E,94.9C |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
2954367 |
September 1960 |
Vandenberg |
3058963 |
October 1962 |
Vandenberg |
3642760 |
February 1972 |
Baekelmans et al. |
3801558 |
April 1974 |
Fletcher et al. |
|
Foreign Patent Documents
Primary Examiner: Smith; Edward J.
Attorney, Agent or Firm: Hill, Gross, Simpson, Van Santen,
Steadman, Chiara & Simpson
Claims
What is claimed is:
1. A process for the production of polyolefins which comprises
polymerizing or copolymerizing olefins in the presence of a
composite catalyst consisting essentially of:
a product of reaction between an ether solution of an
organomagnesium compound and a titanium compound, said ether being
the sole solvent in the reaction system, at a temperature of at
least about 100.degree.C, with the molar ratio of titanium to
magnesium at least about 3 to 1, said titanium compound being
defined by the general formula, Ti(OR).sub.n X.sub.4.sub.-N,
wherein R is selected from the class consisting of alkyl, allyl,
aryl and aralkyl groups, wherein X is a halogen, and wherein n is a
whole number of from 0 to 4 inclusive; and
an organoaluminum compound.
2. A process as defined in claim 1, wherein said organomagnesium
compound is selected from Grignard compounds which are defined by
the general formula, R.sub.1 MgX OR.sub.2 R.sub.3, wherein X is a
halogen, and wherein each of R.sub.1, R.sub.2 and R.sub.3 is
selected from the class consisting of alkyl, allyl, aryl and
aralkyl groups of 1 to 8 carbon atoms.
3. A process as defined in claim 2, wherein R.sub.2 and R.sub.3 are
identical.
4. A process as defined in claim 3, wherein said Grignard compounds
include the complex compounds formed by the union of an ether of 2
to 32 carbon atoms with one of the following methyl magnesium
chloride, methyl magnesium bromide, methyl magnesium iodide,
n-propyl magnesium chloride, n-propyl magnesium bromide, n-propyl
magnesium iodide, n-butyl magnesium chloride, n-butyl magnesium
bromide, n-butyl magnesium iodide, isobutyl magnesium chloride,
isobutyl magnesuim bromide, isobutyl magnesium iodide, hexyl
magnesium chloride, hexyl magnesium bromide, hexyl magnesium
iodide, octyl magnesium chloride, octyl magnesium bromide, phenyl
magnesium chloride, and phenyl magnesium bromide.
5. A process as defined in claim 4, wherein said ether is selected
from the class consisting of dimethyl ether, diethyl ether,
diisopropyl ether, dibutyl ether, methylethyl ether, diallyl ether,
tetrahydrofuran, dioxane, and anisole.
6. A process as defined in claim 1, wherein said titanium compound
is titanium tetrachloride or titanium tetraiodide.
7. A process as defined in claim 1, wherein said titanium compound
is selected from the class consisting of titanium
monomethyoxytrichloride, titanium dimethoxydichloride, titanium
trimethyoxymonochloride, titanium tetramethoxide, titanium
monoethyoxytribromide, titanium monoethyoxytrichloride, titanium
diethoxydichloride, titanium triethoxymonochloride titanium
tetraethoxide, titanium diethoxydibromide, titanium
monobutoxytrichloride, titanium dibutoxydichloride, tianium
tributoxymonochloride, titanium tetrabutoxide, titanium
dibutoxydibromide, titanium monoethoxymonobutoxydichloride,
titanium diethyoxydibutoxide, titanium monopentoxytrichloride,
titanium monophenoxytrichloride, titanium diphenoxydichloride,
titanium triphenoxymonochloride, titanium tetraphenoxide, titanium
diphenoxydibromide, and titanium
monoethyoxymonophenoxydichloride.
8. A process as defined in claim 1, wherein said organoaluminum
compound is selected from the class consisting of trimethyl
aluminum, triethyl aluminum, triisobutyl aluuminum, trihexyl
aluminum, diethyl aluminum monochloride, ethyl aluminum
sesquichloride, and admixtures of the listed compounds.
9. A process as defined in claim 8, wherein said organoaluminum
compound is used in amounts of from about 0.1 to 1,000 times
greater in molar ratio than the product of reaction between the
organomagnesium compound and the titanium compound.
10. A process as defined in claim 1, wherein said process is
adaptable specifcally for the production of a copolymer of ethylene
and another olefin selected from the class consisting of propylene
and 1-butene, said other olefin being contained in said copolymer
in an amount of not more than about 10 molar percent.
Description
BACKGROUND OF THE INVENTION
This invention relates to a process for the production of
polyolefins and is more specifically directed to catalysts for use
in such process.
Since Ziegler's discovery that catalysts composed of organometallic
compounds and transistion metal compounds are well suited for use
in the polymerization process of olefins, numerous similar
catalysts have been advanced for olefin polymerization. It is now
required industrially that the activity of the catalysts for use in
the olefin polymerization processes be so high that no extra steps
are necessitated for removal of catalyst residues. Apparently, a
great majority of the known Ziegler catalysts do not exhibit
sufficiently high activity to meet this requirement.
Japanese Patent Publication No. 35-495 and British Pat. No.
1,030,770, for example, disclose composite catalysts such that
organoaluminum compounds are used in combination with Ziegler
catalysts composed of organomagnesium compounds and transition
metal compounds. While these known composite catalysts certain
exhibit fairly high activity when used for olefin polymerization,
they are still incapable of fulfilling the aforementioned
requirement.
According to Belgian Pat. No. 744,470, high catalytic activity in
the processes of olefin polymerization is realizable by use of a
catalyst resulting from the reaction at relatively low temperatures
of titanium tetrachloride and organomagnesium compounds having a
relatively long alkyl group with 8 to 12 carbon atoms. However,
such organomagnesium compounds having a long alkyl group are
usually expensive, and it is not economically advantageous to
conduct the reaction between organomagnesium compounds and titanium
tetrachloride, which is exothermic, at low temperatures as advanced
by the cited Belgian patent. This catalyst is further
unsatisfactory in terms of the bulk specific gravity of the
resulting polyethylene.
SUMMARY OF THE INVENTION
In view of the noted deficiencies of the prior art, it is an object
of this invention to provide a novel and improved process for the
production of polyolefins by use of a composite catalyst which
exhibits such high activity that the troublesome operation
conventionally required for removal of catalyst residues is
obviated.
Another object of the invention is to provide a composite catalyst
for use in the olefin polymerization process such that, for
example, there can be obtained polyethylene of extremely high bulk
density.
A feature of the invention resides in the use of a composite
catalyst consisting essentially of an organoaluminum compound and
the product of reaction between an organomagnesium compound and a
titanium compound, the reaction being conducted in the presence of
an ether compound at a temperature of at least about 100.degree.C
and with the molar ratio of titanium to magnesium at least about 3
to 1.
Another feature of the invention is that the aforesaid
organomagnesium compound can be easily prepared by reaction, in the
presence of an ether compound, between magnesium and an alkyl,
allyl or aryl halide whereby the compound is obtainable in the form
of a highly dense solution.
A further feature of the invention is that the organomagnesium
compound can be provided in the form of any one of what are herein
referred to as Grignard compounds which are complex compounds
consisting of specifiable magnesium compounds and specifiable
ethers.
A solid catalyst obtained in the form of fine grains as a result of
the above mentioned reaction between organomagnesium compound and
titanium compound is purple or redish purple in color, as compared
with the brown or blackish brown color of the conventional
catalysts used for like purposes. While the exact reasons for this
are not yet ascertained, it is surmised that the crystal structure
of the solid catalyst according to the invention is considerably
different from those of the conventional catalysts.
Further according to this invention, the organomagnesium compounds
employable for the desired reaction with the titanium compounds may
be those having a lower hydrocarbon residue of 1 to 8 carbon atoms
or, if required, those having a lower alkyl group of 1 to 4 carbon
atoms. The organomagnesium or Grignard compounds having such lower
alkyl group are generally very inexpensive and can be prepared
highly efficiently. Moreover, according to the invention, the
organomagnesium compounds which have been prepared in the presence
of ethers or ether compounds can be put to direct use in the
reaction with the titanium compounds. This is a great advantage
over the mentioned British Pat. No. 1,030,770 and Belgian Pat. No.
744,470 which require that the reaction between organomagnesium
compounds and titanium tetrachloride be conducted in the absence of
ethers.
It will therefore be understood that highly active catalysts are
prepared according to the invention by means which have heretofore
been considered disadvantageous and, furthermore, the use of these
catalysts results in the production of polyethylene of extremely
high bulk density, as hereinafter explained in more detail.
The features which are considered novel and characteristic of this
invention are set forth in the appended claims. The invention
itself, however, as well as the further objects and advantages
thereof, will be best understood from the following detailed
description.
DETAILED DESCRIPTION OF THE INVENTION
The organomagnesium compounds for use for the preparation of the
solid catalysts according to the invention, which catalysts are put
to combined use with organoaluminum compounds in olefin
polymerization process, are easily obtainable in the usual manner.
For example, magnesium may be caused to react with alkyl, aryl or
allyl halide in the presence of an ether compound of 2 to 32 carbon
atoms, or with the ether compounds used as a solvent, at a
temperature ranging from about 0.degree. to 100.degree.C. The
magnesium and the alkyl, aryl or allyl halide in use can be in the
molar ratio of approximately 1 to 1, or more desirably the molar
quantity of the latter may be slightly in excess of that of the
former. The reaction can be expedited by use of an activator such
for example as iodine.
According to this invention, the organomagnesium compounds thus
formed is subjected to reaction with titanium compounds. The molar
ratio of titanium to magnesium used in this reaction is required to
be not less than about 3 to 1 or, preferably, to be anywhere
between about 5 to 1 and 100 to 1. The reaction can be carried out
either by introducing the titanium compound to the organomagnesium
compound or vice versa, and at a temperature of at least about
100.degree.C or, preferably, from about 130.degree. to
300.degree.C. The reaction will be further faciliated if the
titanium compound is caused to reflux.
In case the reaction between organomagnesium compound and titanium
compound is conducted at room temperature, the resulting product
will be in the form of solid lumps of varying sizes that are
blackish brown in color. No favorable results will be obtainable if
this reaction product is used directly as a constituent of the
composite catalyst according to the invention. When the product is
heated, however, there can be obtained a highly active,
purple-colored granular catalyst constituent. It may be noted that
even when the reaction is effected at sufficienty elevated
temperatures, the product will be in the form of lumps that are not
finely dispersible and hence will not be suitable for use as a
catalyst in any polymerization process if the molor ratio of
titanium to magnesium in use in the reaction is appreciably less
that 3 to 1.
While the reaction between organomagnesium compound and titanium
compound may be conducted in the presence of no solvent, the use of
the same ether compound as that employed for the preparation of the
organomagnesium compound is desirable. Upon completion of the
reaction any unreacted titanium compound, ether compound and so
forth should be removed by distillation or filtration.
Alternatively, an inert hydrocarbon such for example as pentane,
hexane or heptane may be added to cause sedimentation of suspended
matter, and the liquid is succeedingly decanted for removal of the
unreacted substances. This proceduure may be repeated several
times. In either way the removal of at least the unreacted titanium
compound is desirable. The solid catalyst thus prepared in the form
of finely divided grains can be put to direct use or, if required,
through an additional process of pulverization.
The organomagnesium compounds employable for the preparation of the
solid catalyst that is used in combination with an organoaluminum
compound for the production of polyolefins according to the
invention are defined by the general formula, R'R"Mg, where each of
R' and R" is an alkyl, allyl, aryl or aralkyl group with 1 to 8
carbon atoms, R' and R" being either identical or different.
Preferably, however, the organomagnesium compounds can be provided
in the form of Grignard compounds which within the meaning of this
invention are defined by the general formula, R.sub.1 MgX.sup..
OR.sub.2 R.sub.3, where X is a halogen atom, and each of R.sub.1,
R.sub.2 and R.sub.3 is an alkyl, allyl, aryl or aralkyl group with
1 to 8 carbon atoms, R.sub.2 and R.sub.3 being either identical or
different. The coordination number of the ether with respect to the
RMgX is usually 2, although this is subject to change under varying
conditions.
It may be noted that by the term "Grignard compounds" as used in
this specification and the appended claims are meant all those
prepared in the presence of ethers. Typical examples of such
Grignard compounds include the complex compounds formed by the
union of an ether and any one of such compounds as methyl magnesium
chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl
magnesium chloride, ethyl magnesium bromide, ethyl magnesium
iodide, n-propyl magnesium chloride, n-propyl magnesium bromide,
n-propyl magnesium iodide, n-butyl magnesium chloride, n-butyl
magnesium bromide, n-butyl magnesium iodide, isobutyl magnesium
chloride, isobutyl magnesium bromide, isobutyl magnesium iodide,
hexyl magnesium chloride, hexyl magnesium bromide, hexyl magnesium
iodide, octyl magnesium chloride, octyl magnesium bromide, phenyl
magnesium chloride, and phenyl magnesium bromide.
The ether employable for the formation of such complex compounds
has usually 2 to 32 carbon atoms and is selected from the class
including dimethyl ether, diethyl ether, diisopropyl ether, dibutyl
ether methylethyl ether, diallyl ether, tetrahydrofuran, dioxane,
and anisole. These ethers are of course employable as the solvents
for the preparation of the organomagnesium compounds.
The titanium compounds used for reaction with the organomagnesium
or Grignard compounds under the specified conditions in accordance
with the invention are defined by the general formula, Ti(OR).sub.n
X.sub.4-n, where R is an alkyl, allyl, aryl or aralkyl group,
preferably with 1 to 20 carbon atoms, X is a halogen atom, and n is
a whole number of from 0 to 4 inclusive. In case n is 0, the
formular represents titanium tetrahalides such as titanium
tetrachloride and titanium tetraiodide. It is more desirable,
however, that n be an integer of from 1 to 4 inclusive, that is,
that titanium alkoxide halides be employed as the titanium
compounds to be subjected to reaction with the organomagnesium or
Grignard compounds. The titanium alkoxide halides can be easily
prepared by heating titanium tetrahalide in admixture with alcohols
or phenols. There are, for example, titanium
monomethoxytrichloride, titanium dimethoxydichloride, titanium
trimethoxymonochloride, titanium tetramethoxide, titanium
monoethoxytribromide, titanium monoethoxytrichloride, titanium
diethoxydichloride, titanium triethoxymonochloride, titanium
tetraethoxide, titanium diethoxydibromide, titanium
monobutoxytrichloride, titanium dibutoxydichloride, titanium
tributoxymonochloride, titanium tetrabutoxide, titanium
dibutoxydibromide, titanium monoethoxymonobutoxydichloride,
titanium diethoxydibutoxide, titanium monopentoxytrichloride,
titanium monophenoxytrichloride titanium diphenoxydichloride,
titanium triphenoxymonochloride, titanium tetraphenoxide, titanium
diphenoxydibromide, and titanium
monoethoxymonophenoxydichloride.
Further according to this invention, the products of reaction
between the organomagnesium compounds or Grignard compounds and the
titanium compounds are put to combined use with organometallic
compounds as a composite catalyst for use in the polymerization or
copolymerization of olefins. Usually, the organometallic compounds
can be those in Groups I to III of the periodic table that are used
as the organometallic compounds constituting Ziegler catalysts.
More desirable as such organometallic compounds, however, are the
organoaluminum compounds defined by the general formulae:
R.sub.3 Al, R.sub.2 AlX, RAlX.sub.2, R.sub.2 AlOR,
RAl(OR)X, and R.sub.3 Al.sub.2 X.sub.3
where R is the alkyl or aryl group and X is the halogen atom.
Typical examples of such organoaluminum compounds include trimethyl
aluminium, triethyl aluminum, triisobutyl aluminum, trihexyl
aluminum, diethyl aluminum monochloride, ethyl aluminum
sesquichloride, and various admixtures of these compounds. These
organometallic or organoaluminum compounds are used in amounts from
about 0.1 to 1,000 times greater in molar ratio than the aforesaid
reaction products of the organomagnesium compounds or Grignard
compounds and the titanium compounds.
The production of polyolefins by use of the composite catalyst
prepared as hereinbefore described according to the invention can
be carried out in substantially the same manner as the well known
olefin polymerization process by use of the Ziegler catalysts. More
specifically, the polymerization reaction must be conducted in an
atmosphere substantially completely devoid of oxygen, water and so
forth, or in the state of suspension or solution in a suitable
inert solvent. Employable as such solvent or dispersing agent are
inert hydrocarbons with a carbon number of from about 3 to 20, such
for example as pentane, hexane, heptane, and other n-paraffins.
Other conditions for olefin polymerization include a temperature of
from about 20.degree. to 300.degree.C, preferably from about
50.degree. to 200.degree.C, and a pressure of from about normal
pressure to 100kg/cm.sup.2, preferably from about 2 to
60kg/cm.sup.2. The molecular weight of the resulting polymer is
regulatable to some extent by changing the polymerization
conditions such as temperature and the quantities of the catalysts
in use, but more precisely by the addition of a well calculated
quantity of hydrogen in the polymerization admixture.
The process of this invention is applicable to the production of
all olefins that have been polymerizable conventionally by use of
Ziegler catalysts, and more specifically to the polymerization of
alpha-olefins such as ethylene, propylene and 1-butene and to the
copolymerization of ethylene and propylene, ethylene and 1-butene,
and propylene and 1-butene. Most desirably, however, the inventive
process may be applied to the production of ethylene copolymers
including less than about 10 molar per cent of propylene or
butene.
The invention is hereinafter described more specifically in terms
of several specific Examples thereof together with Comparative
Examples that are given by way of clarification of the advantages
of the invention. It is to be understood that all the succeeding
Inventive Examples are intended purely to illustrate and explain
the invention and not to impose limitations thereon.
INVENTIVE EXAMPLE I
Catalyst Preparation
A 500-milliliter flask equipped with an agitator was filled with
33.3 milliliters (0.1 mole) of the diethyl ether solution (3
mole/liter) of ethyl magnesium bromide, and this solution while
being agitated was admixed with 80 milliliters (0.73 mole) of
titanium tetrachloride. The molar ratio of titanium to magnesium
was thus 7.3 to 1. The reaction first resulted in the production of
relatively small, black-colored lumps. This initial reaction
product was further subjected to reaction for 3 hours at elevated
temperatures and with the titanium tetrachloride in reflux,
whereupon the lumps were thoroughly converted into finely divided
grains that were purple in color and highly dispersible. The final
reaction product was then cooled and was succeedingly admixed with
a large quantity of hexane thereby causing sedimentation of the
dispersed grains. The entire admixture was further allowed to stand
until all the fine grains were settled at the bottom, and the
supernatant liquid was then decanted. This procedure of rinsing
operation was repeated until all the unreacted titanium
tetrachloride was eliminated, and the hexane used as the rinsing
liquid was finally removed by distillation to obtain a solid
catalyst in the form of purple colored, fine grains.
Polymerization
A nitrogen-purged, stainless steel-made, 2-liter autoclave equipped
with agitator was charged with 1,000 milliliters of hexane and then
with 10 millimoles of triethyl aluminum and 408 milligrams of the
purple colored solid catalyst prepared as above stated. The entire
mixture was agitated and heated to a temperature of 90.degree.C.
The mixture was subject to a pressure of 2 kilograms per square
centimeter due to the vapor pressure of the hexane, and the
autoclave was further charged with hydrogen to a total pressure of
6 kilograms per square centimeter and then with ethylene to a total
pressure of 10 kilograms per square centimeter to initiate the
polymerization reaction. The reaction was caused to proceed for 15
minutes, with continuous introduction of ethylene to maintain the
total pressure of 10 kilograms per square centimeter. Upon lapse of
the 15-minute period there was obtained a polymeric slurry, which
slurry was then charged into a beaker, and the hexane was removed
at reduced pressure. Hence, there was obtained 331 grams of
polyethylene which was white in color and which had a melt index of
22.3. Catalytic activity was so high that there were produced 6,660
grams of polyethylene per gram of titanium per hour per ethylene
pressure and 811 grams of polyethylene per gram of solid catalyst
per hour per ethylene pressure. The bulk specific gravity of the
polyethylene produced as above was as high as 0.39.
COMPARATIVE EXAMPLE I
The solid catalyst was prepared in exactly the same way as in
Inventive Example I except that the reaction between titanium
tetrachloride and the diethyl ether solution of ethyl magnesium
bromide was conducted at a temperature of 25.degree.C. The
resulting catalyst was in the form of a black colored solid
consisting mostly of relatively small lumps. This catalyst was
employed in combination with triethyl aluminum for production of
polyethylene by the process of the preceding Inventive Example.
Catalytic activity was so low that there were only 1,130 grams of
polyethylene per gram of titanium per hour per ethylene pressure
and 126 grams of polyethylene per gram of solid catalyst per hour
per ethylene pressure.
COMPARATIVE EXAMPLE II
The solid catalyst was prepared in exactly the same way as in
Inventive Example I except that the reaction between titanium
tetrachloride and the diethyl ether solution of ethyl magnesium
bromide was conducted at a temperature of 25.degree.C and with the
molar ratio of titanium to magnesium 1 to 1. The resulting catalyst
was in the form of relatively large lumps. Extremely low activity
was exhibited when this catalyst was used in combination with
triethyl aluminum for production of polyethylene by the process of
Inventive Example I.
COMPARATIVE EXAMPLE III
The solid catalyst was again prepared in exactly the same way as in
Inventive Example I except that the reaction between titanium
tetrachloride and the diethyl ether solution of ethyl magnesium
bromide was effected with the molar ratio of titanium to magnesium
2 to 1. The resulting catalyst was in the form of a black colored
solid consisting mostly of relatively large lumps. Extremely low
activity was exhibited when this catalyst was used in combination
with triethyl aluminum for production of polyethylene by the
process of Inventive Example I.
INVENTIVE EXAMPLE II
The solid catalyst of Comparative Example III was further admixed
with 80 milliliters of titanium tetrachloride, and the reaction was
caused to proceed for 5 hours with the titanium tetrachloride
refluxed. The black colored lumps were thus gradually caused to
sediment in the form of purple colored, fine grains. The
polymerization reaction was then conducted in exact accordance with
the process of Inventive Examples I except that 216 milligrams of
the solid catalyst formed in the form of fine grains as above was
employed, and that the reaction was caused to proceed for 20
minutes. There was obtained 256 grams of polyethylene which were
white in color and which had a melt index of 19.5. Catalytic
activity was remarkable, with yields of 7,220 grams of polyethylene
per gram of titanium per hour per ethylene pressure and 890 grams
of polyethylene per gram of solid catalyst per hour per ethylene
pressure. The bulk specific gravity of the thus-produced
polyethylene was also as high as 0.39.
INVENTIVE EXAMPLE III
The solid catalyst was prepared in exact accordance with the
process of Inventive Example I except that the diethyl ether
solution of ethyl magnesium bromide was replaced by that of n-butyl
magnesium chloride. The resulting catalyst was in the form of fine
grains that were purple in color. The polymerization reaction was
also conducted in conformity with the details set forth in
Inventive Example I except that 308 milligrams of the above
obtained catalyst was used and that the partial pressure of
hydrogen gas was caused to be 2 kilograms per square centimeter and
that of ethylene 6 kilograms per square centimeter. The reaction
was caused to proceed for 10 minutes, whereupon there was obtained
213 grams of white colored polyethylene with a melt index of 0.3.
Catalytic activity was satisfactory, with yields of 4,500 grams of
polyethylene per gram of titanium per hour per ethylene pressure
and 692 grams of polyethylene per gram or solid catalyst per hour
per ethylene pressure.
INVENTIVE EXAMPLE IV
The solid catalyst was again prepared in exact accordance with the
process of Inventive Example I except that the diethyl ether
solution of ethyl magnesium bromide was replaced by that of n-butyl
magnesium chloride and that 160 milliliters (1.46 moles) of
titanium tetrachloride was used. The molar ratio of titanium to
magnesium was thus 14.6 to 1. The resulting catalyst was in the
form of fine grains that were purple in color. The polymerization
reaction was conducted in conformity with the process of Inventive
Example III except that 241 milligrams of the above prepared
catalyst was used. The reaction was caused to proceed for 10
minutes, and 196 grams of white colored polyethylene was obtained.
Catalytic activity was such that there were yields of 5,300 grams
of polyethylene per gram of titanium per hour per ethylene pressure
and 814 grams of polyethylene per gram of solid catalyst per hour
per ethylene pressure.
INVENTIVE EXAMPLE V
The solid catalyst was prepared in exact accordance with the
process of Inventive Example I except that diethyl ether as the
solvent was removed from the diethyl ether solution of ethyl
magnesium bromide before this is subjected to reaction with
titanium tetrachloride. The polymerization reaction was also
conducted in exact accordance with the process of Inventive Example
I except that 356 milligrams of the above prepared solid catalyst
was used and that the reaction was caused to proceed for 20
minutes. There was obtained 348 grams of white colored polyethylene
with a melt index of 20.0. Catalytic activity was extremely high
with yields of 6,150 grams of polyethlene per gram of titanium per
hour per ethylene pressure and 735 grams of polyethylene per gram
of solid catalyst per hour per ethylene pressure.
INVENTIVE EXAMPLE VI
The solid catalyst was prepared in exact accordance with the
process of Inventive Example I except that the titanium
tetrachloride was first charged into the flask, followed by the
diethyl solution of ethyl magnesium bromide. The polymerization
reaction was also conducted in exact accordance with the process of
Inventive Example I except that 210 milligrams of the above
prepared solid catalyst was used and that the reaction was caused
to proceed for 20 minutes. There was obtained 218 grams of white
colored polyethylene with a melt index of 21.6. Catalytic activity
was extremely high with yields of 6,410 grams of polyethylene per
gram of titanium per hour per ethylene pressure and 780 grams of
titanium per gram of solid catalyst per hour per ethylene
pressure.
INVENTIVE EXAMPLE VII
The solid catalyst was prepared in exact accordance with the
process of Inventive Example III except that the diethyl ether
solution of butyl magnesium chloride was replaced by that of hexyl
magnesium chloride and that 110 milliliters (0.1 mole) of titanium
tetrachloride was used. The polymerization reaction was conducted
by use of 192 milligrams of the thus-prepared solid catalyst in
conformity with the process of Inventive Example III. Upon lapse of
20 minutes there was obtained 270 grams of white colored
polyethylene. Catalytic activity was such that there were yields of
4,580 grams of polyethylene per gram of titanium per hour per
ethylene pressure and 703 grams of polyethylene per gram of solid
catalyst per hour per ethylene pressure.
INVENTIVE EXAMPLE VIII
Copolymerization reaction was conducted by use of the autoclave set
forth in Inventive Example I, which autoclave was charged with 153
milligrams of the solid catalyst of Inventive Example I, 10
millimoles of triethyl aluminum, and 1,000 milliliters of hexane.
After further introducing hydrogen to a pressure of 1.5 kilograms
per square centimeter, a mixed ethylene-propylene gas containing 2
molar per cent of propylene was supplied at a temperature of
80.degree.C. The reaction was caused to proceed for 30 minutes
while the pressure of the autoclave was maintained at 7 kilograms
per square centimeter. There was resultantly obtained 265 grams of
white colored ethylene-propylene copolymer, which was succeedingly
confirmed to be as such by infrared spectrum techniques.
INVENTIVE EXAMPLE IX
Catalyst Preparation
A nitrogen-purged, 500-milliliter flask equipped with an agitator
was filled with 94 grams (0.45 mole) of titanium
diethyoxydichloride, and 30 milliliters (0.09 mole) of the diethyl
ether solution (3 mole/liter) of ethyl magnesium bromide was
succeedingly dropped into the flask by means of a tap funnel over a
30-minute period. The molar ratio of titanium to magnesium was thus
5 to 1. There were first produced relatively small, black colored
lumps, and the reaction was caused to proceed another 3 hours at a
temperature of 130.degree.C, whereupon the lumps were thoroughly
converted into fine grains that were purple in color and highly
dispersible. This final reaction product was succeedingly admixed
with a large quantity of hexane thereby causing sedimentation of
the dispersed grains, and the liquid was then decanted. The
decantation process was repeated until all the unreacted titanium
compound was eliminated, and the hexane used as the rinsing liquid
was finally removed by distillation to obtain a solid catalyst in
the form of purple colored, fine grains.
Polymerization
A nitrogen-purged, stainless steel-made, 2-liter autoclave equipped
with an agitator was charged with 1,000 milliliters of hexane and
then with 5 millimoles of triethyl aluminum and 146 milligrams of
the purple colored solid catalyst prepared as in the foregoing. The
entire mixture was agitated and heated to a temperature of
90.degree.C. The mixture was subject to a pressure of 2 kilograms
per square centimeter due to the vapor pressure of the hexane in
use, and the autoclave was further charged with hydrogen to a total
pressure of 4.4 kilograms per square centimeter and then with
ethylene to a total pressure of 10 kilograms per square centimeter
to initiate the polymerization reaction. The reaction was caused to
proceed for 10 minutes, with continuous introduction of ethylene to
maintain the total pressure of 10 kilograms per square centimeter.
Upon lapse of the 10-minute period there was obtained a polymeric
slurry, which slurry was then charged into a beaker, and the hexane
was removed at reduced pressure. Hence, 198 grams of polyethylene
was obtained which was white in color and which had a melt index of
0.21. Catalytic activity was extremely high with yields of 11,500
grams of polyethylene per gram of titanium per hour per ethylene
pressure and 1,451 grams of polyethylene per gram of solid catalyst
per hour per ethylene pressure.
COMPARATIVE EXAMPLE IV
The solid catalyst was prepared in exactly the same way as in
Inventive Example IX except that the reaction between titanium
diethoxydichloride and the diethyl ether solution of ethyl
magnesium bromide was conducted at a temperature of 25.degree.C.
The resulting catalyst was in the form of a black colored solid
consisting mostly of relatively small lumps and was thus noticeably
different from that prepared in Inventive Example IX. The
polymerization reaction was also conducted in exact accordance with
the process of Inventive Example IX except that 250 milligrams of
the black colored solid catalyst was used and that the reaction was
caused to proceed for 30 minutes. Catalytic activity was
undoubtedly inferior, with yields of only 900 grams of polyethylene
per gram of titanium per hour per ethylene pressure and 102 grams
of polyethylene per gram of solid catalyst per hour per ethylene
pressure.
COMPARATIVE EXAMPLE V
The solid catalyst was prepared in exact accordance with the
process of Inventive Example IX except that the reaction between
titanium diethoxydichloride and the diethyl ether solution of ethyl
magnesium bromide was carried out with the molar ratio of titanium
to magnesium 2 to 1. The resulting catalyst was mostly in the form
of black colored, relatively small lumps. Extremely low activity
was exhibited when this catalyst was employed for polyethylene
production in substantial accordance with the process of Inventive
Example IX.
INVENTIVE EXAMPLE X
The solid catalyst was prepared in exact accordance with the
process of Inventive Example IX except that 137 grams (0.45 mole)
of titanium diphenoxydichloride was used instead of 94 grams (0.45
mole) of titanium diethoxydichloride. The polymerization reaction
was also conducted in exact accordance with the process of
Inventive Example IX except that 71 milligrams of the thus prepared
catalyst was used. There was resultantly obtained 124 grams of
white colored polyethylene with a melt index of 0.19. Catalytic
activity was remarkably high with yields of 15,400 grams of
polyethylene per gram of titanium per hour per ethylene pressure
and 1,870 grams of polyethylene per gram of solid catalyst per hour
per ethylene pressure.
INVENTIVE EXAMPLE XI
The solid catalyst was prepared in exact accordance with the
process of Inventive Example IX except that 204 grams (0.9 mole) of
titanium n-butoxytrichloride was used instead of 94 grams (0.45
mole) of titanium diethoxydichloride. The polymerization reaction
was also conducted in exact accordance with the process of
Inventive Example IX except that 143 milligrams of the resulting
catalyst was used. There was thus obtained 166 grams of white
colored polyethylene with a melt index of 0.09. Catalytic activity
was extremely high with yields of 10,500 grams of polyethylene per
gram of titanium per hour per ethylene pressure and 1,240 grams of
polyethylene per gram of solid catalyst per hour per ethylene
pressure.
INVENTIVE EXAMPLE XII
The solid catalyst was prepared in exact accordance with the
process of Inventive Example IX except that ethyl magnesium bromide
was replaced by butyl magnesium chloride. The polymerization
reaction was also conducted in exact accordance with the process of
Inventive Example IX except that 156 milligrams of the thus
prepared catalyst was used. There was resultantly obtained 197
grams of white colored polyethylene with a melt index of 0.14.
Catalytic activity was high with yields of 9,500 grams of
polyethylene per gram of titanium per hour per ethylene pressure
and 1,350 grams of polyethylene per gram of solid catalyst per hour
per ethylene pressure.
INVENTIVE EXAMPLE XIII
Copolymerization reaction was conducted by use of the autoclave set
forth in Inventive Example IX, which autoclave was with charged 96
milligrams of the solid catalyst of Inventive Example IX, 5
millimoles of triethyl aluminum, and 1,000 milliliters of hexane.
Hydrogen was further introduced into the autoclave to a pressure of
1.5 kilograms per square centimeter, and then a mixed
ethylene-propylene gas containing 2 molar percent of propylene was
supplied at a temperature of 80.degree.C. The copolymerization
reaction was caused to proceed for 15 minutes while the autoclave
pressure was maintained at 7 kilograms per square centimeter. As a
result there was obtained 120 grams of white colored
ethylene-propylene copoler, which was succeedingly confirmed to be
as such by infrared spectrum techniques. Catalytic activity was
satisfactory with yields of 7,650 grams of copolymer per gram of
titanium per hour per ethylene pressure and 890 grams of copolymer
per gram of solid catalyst per hour per ethylene pressure.
While the invention has been described hereinbefore in very
specific aspects thereof, many modifications or changes will
readily be contemplated by the specialists, without necessarily
departing from the spirit and scope of the invention as sought to
be defined by the following claims.
* * * * *